CN106477587A - Preparation method of silica gel for polyolefin catalyst carrier - Google Patents
Preparation method of silica gel for polyolefin catalyst carrier Download PDFInfo
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- CN106477587A CN106477587A CN201510527284.4A CN201510527284A CN106477587A CN 106477587 A CN106477587 A CN 106477587A CN 201510527284 A CN201510527284 A CN 201510527284A CN 106477587 A CN106477587 A CN 106477587A
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 65
- 239000000741 silica gel Substances 0.000 title claims abstract description 52
- 229910002027 silica gel Inorganic materials 0.000 title claims abstract description 52
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- 239000003054 catalyst Substances 0.000 title claims abstract description 17
- 229920000098 polyolefin Polymers 0.000 title claims abstract description 15
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims abstract description 43
- 238000006243 chemical reaction Methods 0.000 claims abstract description 35
- 238000000034 method Methods 0.000 claims abstract description 21
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000007788 liquid Substances 0.000 claims abstract description 13
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 7
- 150000007522 mineralic acids Chemical class 0.000 claims abstract description 5
- 229960001866 silicon dioxide Drugs 0.000 claims description 47
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 38
- 239000002253 acid Substances 0.000 claims description 31
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 31
- 239000011707 mineral Substances 0.000 claims description 31
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- 239000012153 distilled water Substances 0.000 claims description 11
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 8
- 235000019353 potassium silicate Nutrition 0.000 claims description 6
- 239000000377 silicon dioxide Substances 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
- 239000011261 inert gas Substances 0.000 claims description 5
- 230000004044 response Effects 0.000 claims description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 239000001117 sulphuric acid Substances 0.000 claims description 4
- 235000011149 sulphuric acid Nutrition 0.000 claims description 4
- 239000004115 Sodium Silicate Substances 0.000 claims description 3
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- 239000004111 Potassium silicate Substances 0.000 claims description 2
- 239000006185 dispersion Substances 0.000 claims description 2
- 239000003292 glue Substances 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- NNHHDJVEYQHLHG-UHFFFAOYSA-N potassium silicate Chemical compound [K+].[K+].[O-][Si]([O-])=O NNHHDJVEYQHLHG-UHFFFAOYSA-N 0.000 claims description 2
- 229910052913 potassium silicate Inorganic materials 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 229910052710 silicon Inorganic materials 0.000 claims description 2
- 239000010703 silicon Substances 0.000 claims description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims 1
- 239000011148 porous material Substances 0.000 abstract description 18
- 239000000499 gel Substances 0.000 abstract description 13
- 230000008569 process Effects 0.000 abstract description 6
- 239000002994 raw material Substances 0.000 abstract description 6
- 230000008901 benefit Effects 0.000 abstract description 4
- 239000002245 particle Substances 0.000 abstract description 3
- 238000004132 cross linking Methods 0.000 abstract description 2
- 239000007863 gel particle Substances 0.000 abstract description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract description 2
- 238000004220 aggregation Methods 0.000 abstract 1
- 230000002776 aggregation Effects 0.000 abstract 1
- 238000009776 industrial production Methods 0.000 abstract 1
- 238000004886 process control Methods 0.000 abstract 1
- 238000012360 testing method Methods 0.000 description 14
- 239000003795 chemical substances by application Substances 0.000 description 5
- 230000004913 activation Effects 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000010792 warming Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 229910052681 coesite Inorganic materials 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 229910052906 cristobalite Inorganic materials 0.000 description 2
- 150000002191 fatty alcohols Chemical class 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 239000011164 primary particle Substances 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 229910052682 stishovite Inorganic materials 0.000 description 2
- 229910052905 tridymite Inorganic materials 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 238000004438 BET method Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052910 alkali metal silicate Inorganic materials 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000002902 bimodal effect Effects 0.000 description 1
- 239000002274 desiccant Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- -1 fatty alcohol amine Chemical class 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000010297 mechanical methods and process Methods 0.000 description 1
- 238000011177 media preparation Methods 0.000 description 1
- 239000000693 micelle Substances 0.000 description 1
- 230000004899 motility Effects 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
Landscapes
- Silicon Compounds (AREA)
- Catalysts (AREA)
Abstract
The invention provides a preparation method of a silica gel carrier for a polyolefin catalyst. The gel is prepared by taking alkaline silica gel, silicate and inorganic acid as raw materials through gel reaction. The preparation process takes alkaline silica sol as reaction base liquid, silicate and inorganic acid are added in a parallel flow mode, and the preparation process of the silica gel carrier is completed by controlling the pH value of a reaction system and combining high-temperature hydrothermal reaction. The method has the advantages that new colloidal particles generated by the reaction of gel and sol in the reaction process directly react with hydroxyl on the surface of the silica sol, and the crosslinking among the colloidal particles is completed through continuous aggregation; and the later-stage high-temperature hydrothermal reaction accelerates the reaction among gel particles, thereby greatly improving the pore volume and the pore diameter of the silica gel. Because the performance of the added silica sol is similar to that of the silica gel, the process control is simple; the method can improve the pore volume and the pore diameter of the silica gel, ensure good process repeatability and bring benefits to industrial production.
Description
Technical field
The present invention relates to a kind of preparation method of silica gel is and in particular to a kind of polyolefin catalyst silica-gel carrier
Preparation method.
Background technology
Silica gel has special pore structure, big specific surface area and excellent heat stability, is extensively used
Make adsorbent, desiccant, chromatograph column support and catalyst carrier.At present, the existing multiple methods of silica gel preparation,
It is most commonly that with silicate and mineral acid as raw material, reaction under certain pH value forms gel, then passes through
Operations such as aging, washing, pickling, drying etc. obtain silica gel.
Polyolefin catalyst silica-gel carrier requires there is suitable specific surface area, pore volume and aperture, for obtaining more
Excellent or specific silica gel physical index, the preparation of silica-gel carrier reports many modified technique schemes.Including with
Mineral acid is bottom liquid, at a certain temperature, is directly added into silicate, or using mineral acid with silicate simultaneously
The mode of stream adds, and the method, primarily to obtaining the silica-gel carrier of bimodal pore distribution, is gone back in preparation process
The physical index of silica-gel carrier can be improved by adding modifying agent and expanding agent, Patents have
US5321105、CN201010283277.1、CN201210365806.1、CN201210366892.8、
CN101624431 (A), CN2011101029361, CN201110419933.0 etc.；Also have with silicate
For bottom liquid, at a certain temperature, it is directly added into mineral acid, or the side using mineral acid and silicate cocurrent
Formula adds, and the method mainly obtains big pore volume, high-specific surface area silica-gel carrier, and Patents have：
CN01131135.5、CN200510117271.6、CN200510129965.1、CN201010287087.7、
CN201110137699.2、US5895770、US4100105、US4892853、US5372983、
EP0505583 etc..It is all right that the numerous patented technologies being formed embody reaction raw materials system, process regulation
The physical index of silica-gel carrier produces material impact.
Inventor is found by research, the various process programs of prior art report, or because in reaction system
Add modifying agent, the component such as expanding agent, or the reason because being difficult to effective control in course of reaction, silica gel is given birth to
The repeatability of production. art can be poor, and is unfavorable for commercial introduction and application.Such as CN201110102936.1,
CN201110419933.0 all discloses a kind of preparation method of macro porous silica gel.CN201110102936.1 be with
Based on adding the primary gel of special alkaline medium preparation under sour environment, make through gel repeatedly and double hydrolysis
With being effectively improved pore structure and the distribution of silica gel, preparing macropore, multimodal and wide distribution silica gel.Specifically
With mineral acid for bottom liquid, first contact with alkaline medium, mineral acid is 0.5～4.0 with the mol ratio of alkaline medium；
Add silicate solutions, treat that first gel moment is formed and stop adding silicate solutions, rapidly join distillation
Water, makes gel disperse under water solution system as far as possible；Continuously add silicate solutions, adjust to pH value of solution
Value=10～12, adds inorganic acid solution, control ph is in pH=7～9 more acidified, washing,
It is dried, roasting obtains silica gel product.But the initial stage gel of the method easily causes that aperture is more, pore divides
The unfavorable problem such as cloth is wide.With regard to this, CN201110419933.0 proposes improvement project, be with silicate,
Mineral acid, alkaline medium, fatty alcohol or fatty alcohol amine are raw material, first with dilute sulfuric acid for bottom liquid, add at 30 DEG C
Enter ammonia, ethanol and n-butyl alcohol, by colloidal sol repeatedly, gel, obtain pore volume through techniques such as subsequent treatment
1.68cm3/g, aperture 20.28, specific surface area is the silica gel product of 331.4m2/g.Inventor is through overtesting
Show, because of the complexity (initial stage forms primary particle, later stage colloidal sol, gel repeatedly) of technical process, or plus
Entering expanding agent (fatty alcohol) leads to the repeatability of technique to be difficult to control to, and the quality stability of silica gel product is poor.
Content of the invention
It is an object of the invention to provide a kind of preparation method of polyolefin catalyst silica-gel carrier.
The present invention provide silica-gel carrier preparation method, be with silicate, mineral acid for raw material through gel reaction,
The operations such as acidifying, water Xian, drying, activation be obtained it is characterised in that：Preparation process includes 1) with alkalescence
Ludox is 5%～15% as bottom liquid, alkaline silica sol with the mass ratio of silicate；2) 30～50
At DEG C, silicate is passed through with mineral acid and stream mode adds, and silicate with the molar concentration rate of mineral acid is
0.2～0.8, stop when reaction system pH is 6～7, add deionized water to carry out rapid dispersion；3)
Add silicate and mineral acid again, both molar concentration rates are 1.2～2.0, question response system pH 10～
Stop when 12, keep constant 1～3 hour；4) reaction system is little in 70～100 DEG C of hydro-thermal reactions 1～5
When.
Specifically, silica gel preparation method of the present invention includes：
1) with 3.0～5.0g alkaline silica sol of pH value 9～10 for bottom liquid, stir and be warming up to 30～
50℃；
2) and stream mode adds silicate and inorganic acid solution, the molar concentration rate of silicate and mineral acid
For 0.2～0.8, the addition flow velocity of silicate and mineral acid is 3～5ml/min, when reaction solution system
PH value reach 6～7 stopping, add deionized water quickly disperseed；
3) silicate and mineral acid are added again, the molar concentration rate of silicate and mineral acid is 1.2～
2.0, the addition flow velocity of adjustment silicate and mineral acid is 5～8ml/min, pH value of reaction system reaches 10～
Stop when 12, isothermal reaction 1～3 hour；
4) be warming up to 70～100 DEG C, preferably 80～90 DEG C, keeping body system at high temperature hydro-thermal reaction 1～
5 hours, preferably 2～4 hours；
5) add mineral acid, question response solution ph is to stop when 3～5, keep system to continue reaction
1～3 hour；
6) reaction system is down to room temperature, is washed with alcohol mixeding liquid using distilled water or distilled water, 300
DEG C～335 DEG C at high temperature drying, 400 DEG C～600 DEG C of inert gas shielding activates 3～6 hours, obtains
Silica-gel carrier.
Mineral acid of the present invention be selected from sulphuric acid, hydrochloric acid, nitric acid one kind at least within, concentration be 1.0～
3.0mol/L.Preferably sulfuric acid, concentration is 0.5～2.5mol/L.
Described silicate is selected from sodium silicate, potassium silicate one kind at least within, or waterglass is (by alkali gold
Belong to the soluble alkali metal silicate that oxide and silicon dioxide are combined into), concentration is 1.0～3.0mol/L.
Preferably waterglass.
Alkaline silica sol can be directly commercially available or self-control obtains.Homemade alkaline silica sol can be using chemistry
The known method such as method and Mechanical Method.Silicon dioxide (SiO in alkaline silica sol2) content 15～40%, pH value 9～
10, mean diameter 8～20nm.
The cocurrent addition speed of described silicate and mineral acid can be identical or different.Flow velocity and each material concentration
There is the motility of matching, adaptability and adjustment.For ease of practical operation, the preferably cocurrent in each stage
Silicate and mineral acid add flow velocity identical.
Using a certain amount of alkaline silica sol as primary particle, silicate and mineral acid adopt cocurrent to add to the present invention
Mode, by controlling the pH value of reaction system, completes the preparation of silica-gel carrier in conjunction with high temperature hydro-thermal reaction
Journey.Its advantage is, the new micelle that reaction carries out middle gel, colloidal sol reaction generates can be directly molten with silicon
The hydroxyl effect on glue surface, completes the crosslinking between sol particles by continuous gathering；Later stage high temperature hydro-thermal is anti-
Should, accelerate the reaction between gel particles, thus significantly improving the pore volume of silica gel, aperture.By being added
Ludox and silica gel similar nature, technology controlling and process is simple；Improve silica gel pore volume, aperture while it is ensured that
Good process repeatability, brings benefit to commercial production.
Specific embodiment
By the following examples the present invention is described in further detail, but these embodiments are not considered as to this
Bright restriction.
Method of testing
Specific surface area：Gas absorption BET method is tested, GB/T19587-2004.
Pore volume：BJH (Barrett-Joyner-Halenda) method is tested, ISO 15901-2.
Average pore size d=4V/A, A is specific surface area, and V is pore volume, and d is aperture.
Raw material
Alkaline silica sol：SiO2Content be 30%, mean diameter 15～20nm, pH value be 9.5～
10, Suzhou Nano Dispersions Co., Ltd. produces
Waterglass：Technical grade, Catalyst Factory of Lanzhou Petrochemical Company produces
Sulphuric acid：Analysis is pure, and Baiyin City, gansu Province Yin Huan chemicals factory produces
Embodiment 1
Alkaline silica sol 4.0g is added in reactor, opens stirring, rotating speed is 18r/min, slow intensification
To 50 DEG C, 1.0mol/L silicate and 1.5mol/L dilute sulfuric acid are added with 3ml/min cocurrent, molten when reacting
When liquid pH value is to 6, distilled water is added so that collosol-gelatum system is thoroughly disperseed；Added with 6ml/min cocurrent
2.0mol/L silicate and 1.5mol/L dilute sulfuric acid, when reacting solution pH value is 12, stops adding and mix
Close liquid, isothermal reaction 2 hours；Slowly reactant liquor is warming up to 90 DEG C, isothermal reaction 3 hours；Quickly
Add 1.5mol/L dilute sulfuric acid, when reacting solution pH value is 3, stop adding dilute sulfuric acid, isothermal reaction
1 hour；Remove heater, be slowly cooled to room temperature, then through distilled water wash three times, at 335 DEG C
It is dried, under inert gas shielding, 600 DEG C of activation obtain silica-gel carrier product in 4 hours.Repeat for three times to try
Testing is 1-1,1-2,1-3, and test result is as shown in table 1.
Embodiment 2
Preparation process, with embodiment 1, except for the difference that adds 3.0g Ludox, other conditions and embodiment 1
Identical.Three times are repeated test is 2-1,2-2,2-3, and silica gel physical property measurement result is as shown in table 1.
Embodiment 3
1.0mol/L silicate and 1.5mol/L dilute sulfuric acid are added with 5ml/min cocurrent, as reaction solution pH
When being worth 6, distilled water is added so that collosol-gelatum system is thoroughly disperseed, other conditions are same as Example 1.
Three times are repeated test is 3-1,3-2,3-3, and silica gel test result is as shown in table 1.
Embodiment 4
Late phase reaction temperature, with embodiment 1, is except for the difference that risen to 80 DEG C, the isothermal reaction time by preparation process
For 4 hours.Three times are repeated test is 4-1,4-2,4-3, and silica gel test result is as shown in table 1.
Embodiment 5
Preparation process with embodiment 1, except for the difference that after the collosol-gelatum system of reaction solution thoroughly disperses with
8ml/min cocurrent adds 2.0mol/L silicate and 1.5mol/L dilute sulfuric acid.Three times are repeated test is 5-1,
5-2,5-3, silica gel test result is as shown in table 1.
Comparative example 1
The sodium silicate solution that 30ml concentration is 1.5mol/L adds in reactor, opens stirring, rotating speed is
18r/min, is to slowly warm up to 50 DEG C, adds 1.0mol/L silicate and 1.5mol/L with 3ml/min cocurrent
Dilute sulfuric acid, when reacting solution pH value is to 6, adds distilled water so that collosol-gelatum system is thoroughly disperseed；With
6ml/min cocurrent adds 2.0mol/L silicate and 1.5mol/L dilute sulfuric acid, when reacting solution pH value is 12
When, stop adding mixed liquor, isothermal reaction 5 hours；Rapidly join 1.5mol/L dilute sulfuric acid, work as reaction
When solution ph is 3, stop adding dilute sulfuric acid；Remove heater, be slowly cooled to room temperature, then
Through distilled water wash three times, it is dried at 335 DEG C, under inert gas shielding, 600 DEG C of activation obtain for 4 hours
Silica-gel carrier product.Three times are repeated test is 6-1,6-2,6-3, and test result is as shown in table 1.
Comparative example 2
By SiO2Content be 30% pH value be 10 alkaline silica sol 4.0g add reactors in, open and stir
Mix, rotating speed is 18r/min, is to slowly warm up to 50 DEG C, 1.0mol/L silicate is added with 3ml/min cocurrent
With 1.5mol/L dilute sulfuric acid, when reacting solution pH value is to 6, distilled water is added to make collosol-gelatum system
Thoroughly disperse；2.0mol/L silicate and 1.5mol/L dilute sulfuric acid are added with 6ml/min cocurrent, works as reaction
When solution ph is 12, stop adding mixed liquor, isothermal reaction 4 hours；Rapidly join dilute sulfuric acid,
When reacting solution pH value is 3, stop adding 1.5mol/L dilute sulfuric acid；Remove heater, slowly cold
But to room temperature, then through distilled water wash three times, it is dried at 335 DEG C, under inert gas shielding, 600
DEG C activation obtains silica-gel carrier product in 4 hours.Three times are repeated test is 7-1,7-2,7-3, test result
As shown in table 1.
Table 1 silica-gel carrier physical property measurement result and stable difference
Note：Stablize difference：Difference between sample test value and sample mean.Sample pore volume, specific surface
Long-pending is that instrument is surveyed, and aperture is to be calculated by formula, therefore, stablizes difference and taking pore volume calculating as a example says
Bright experimental repeatability.
Claims (9)
1. the preparation method of polyolefin catalyst silica-gel carrier is it is characterised in that comprise the following steps：
1) using alkaline silica sol as bottom liquid, alkaline silica sol is 5%～15% with the mass ratio of silicate；
2) at 30～50 DEG C, silicate is passed through with mineral acid and stream mode addition, silicate and mineral acid
Molar concentration rate be 0.2～0.8, question response system pH be 6～7 when stop, add deionized water carry out
Rapid dispersion；
3) silicate and mineral acid are added again, both molar concentration rates are 1.2～2.0, question response system
PH stops when 10～12, keeps constant 1～3 hour；
4) reaction system was in 70～100 DEG C of hydro-thermal reactions 1～5 hour；
5) add mineral acid, question response solution ph is to stop when 3～5, keep system continue reaction 1～
3 hours；
6) reaction system is down to room temperature, is washed with alcohol mixeding liquid using distilled water or distilled water, 300
DEG C～335 DEG C at high temperature drying, 400 DEG C～600 DEG C of inert gas shielding activates 3～6 hours, obtains silicon
Glue carrier.
2. the preparation method of polyolefin catalyst silica-gel carrier according to claim 1, its feature
It is, in step (1), the pH value of described bottom liquid alkaline silica sol is 9～10.
3. the preparation method of polyolefin catalyst silica-gel carrier according to claim 1, its feature
It is, in step (2), the addition flow velocity of described silicate and mineral acid is 3～5ml/min；Step (3)
In, the addition flow velocity of described silicate and mineral acid is 5～8ml/min.
4. the preparation method of polyolefin catalyst silica-gel carrier according to claim 3, its feature
It is, the addition speed of described silicate and mineral acid is identical or different.
5. the preparation method of polyolefin catalyst silica-gel carrier according to claim 1, its feature
It is, in step (4), hydrothermal temperature is 80～90 DEG C, the hydro-thermal reaction time is 2～4 hours.
6. the preparation side of the polyolefin catalyst silica-gel carrier according to any one of claim 1 to 5
Method is it is characterised in that described mineral acid is selected from least in sulphuric acid, hydrochloric acid and the formed group of nitric acid
Kind, described inorganic acid concentration is 1.0～3.0mol/L.
7. the preparation method of polyolefin catalyst silica-gel carrier according to claim 6, its feature exists
In described mineral acid is sulphuric acid, and sulfuric acid concentration is 0.5～2.5mol/L.
8. the preparation side of the polyolefin catalyst silica-gel carrier according to any one of claim 1 to 5
Method it is characterised in that described silicate by waterglass or by sodium silicate and potassium silicate, sodium silicate group in groups
At least one in group, the concentration of described silicate is 1.0～3.0mol/L.
9. the preparation side of the polyolefin catalyst silica-gel carrier according to any one of claim 1 to 5
Method it is characterised in that in described alkaline silica sol dioxide-containing silica be 15～40%, pH value be 9～
10, mean diameter is 8～20nm.
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| CN109833918A (en) * | 2017-11-28 | 2019-06-04 | 中国石油天然气股份有限公司 | Preparation method of carrier silica gel |
| CN109833917A (en) * | 2017-11-28 | 2019-06-04 | 中国石油天然气股份有限公司 | Preparation method of silica gel carrier for loading catalyst |
| CN109836517A (en) * | 2017-11-28 | 2019-06-04 | 中国石油天然气股份有限公司 | Preparation method of silica gel carrier for olefin catalysis |
| CN109833858A (en) * | 2017-11-28 | 2019-06-04 | 中国石油天然气股份有限公司 | Preparation method of carrier silica gel for olefin catalyst |
| CN109835909A (en) * | 2017-11-28 | 2019-06-04 | 中国石油天然气股份有限公司 | Preparation method of modified silica gel carrier |
| CN109835911A (en) * | 2017-11-28 | 2019-06-04 | 中国石油天然气股份有限公司 | Preparation method of silica gel carrier for olefin catalytic loading |
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